Lecture XIX Charged PS’s - Alginates

1. Lecture XIXCharged PS’s - Alginates • Alginic Acid • Alginate salts (Na+,K+,NH4+,Ca++) • Propylene glycol alginates (PGAs)

2. Charged PS’s - Alginates • Sources/Manufacture • Brown Seaweeds - growing areas • Harvesting methods • Manufacturing • Extraction • Ion Exchange

3. M N Macrocystis spp. Nereocystis spp. Areas Known to Support Brown Algae La La La A A La N E M M E E D Le E M M M M A As D Alaria spp. Ascophylum spp. Durvillea spp. E La Le Ecklonia spp. Laminaria spp. Lessonia spp. ATM95 003.00

4. New Weed Harvesters in Ireland and Iceland

7. Recording eco data to improve knowledge of seaweed

9. Kelp canopy Stipes Schematic of Macro kelp plant Fronds Holdfast

13. Wash Digested in Alkali Clarify and Bleach CaCl 2 Acid React with Ammonia Salt React with Propylene Oxide React with Salt Algin Manufacturing Process Wet/Dry Seaweed Washed Weed Crude Alginate Paste Dilute Sodium Alginate Solution CaAlginate Alginic Acid Ammonium Alginate Propylene Glycol Alginate Sodium Alginate Potassium Alginate Calcium Alginate etc..

14. Alginate Conformational Structure COO- OH O OH O O O O OH COO- OH 1,4 a -L-Guluronic Acid OH COO- O O HO O O HO O COO- OH 1,4 ß-D-Mannuronic Acid

15. COOH O O COOH O O OH OH OH OH a-L-Guluronic Acid b-D-Mannuronic Acid M G M M G G M G M M G G M G M M G G Mannuronic Block Guluronic Block Mixed Block Algin Basic Structure Polymer Structure:

16. Unique Properties of Alginic Acid • Sensitive to heat - depolymerizes • Manufacturing, mainly • Insoluble but swells ATM95 012.00

17. Salts of Alginic Acid • Sodium (Na+) most common • Also K+, NH4+, Ca++, and combos ATM95 012.00

18. Unique Properties of Alginate Salts • Gel or Precipitate with Acid • React with Calcium Ions to: —Give Increased Viscosity—Form Heat Stable Gels—Form Insoluble Polymers ATM95 012.00

19. Effect of pH on algin solutions 1.5% Med Ca NaAlginate 2% Low Ca NaAlginate 2% Hi Ester PGA

20. Unique Properties of Alginate Salts • Gel or Precipitate with Acid • React with Calcium Ions to: —Give Increased Viscosity ATM95 012.00

21. COO- O O O O HO OH HO OH OH OH O O COO- COO- Ca++ Ca++ COO- COO- O O O O O HO OH OH OH OH OH O COO- Algin/Calcium Interaction (Simplified Concept)

22. Gelation C B Precipitation Viscosity A [Cross-Linking Agent]

23. sodium-calcium alginate As is Viscosity Sodium Hexametaphosphate Viscosity

25. Unique Properties of Alginate Salts • Gel or Precipitate with Acid • React with Calcium Ions to: —Give Increased Viscosity—Form Heat Stable Gels ATM95 012.00

26. Alginate Conformational Structure COO- OH O OH O O O O OH COO- OH 1,4 a -L-Guluronic Acid OH COO- O O HO O O HO O COO- OH 1,4 ß-D-Mannuronic Acid

27. 2+ +Ca 2+ = Ca = G Block = M or MG Block 2+ -Ca Guluronic Acid Block Association Solution “Egg-Box” Model

28. Calcium Alginate Gel Structure

30. CALCIUM ION CONTROL is the KEY to effective use of the ALGIN/CALCIUM REACTION Kelco CR Sem 4366

31. Algin Gelling Techniques • Diffusion setting • Internal Setting • Setting by cooling ATM95 025.00

32. Diffusion Setting(Extruded Systems) • Simplest Technique • Thin Strips or Small Particles • Calcium Concentration Dependent ATM95 048.00

34. Algin Gelling Techniques • Diffusion setting • Internal Setting • Molded Systems ATM95 025.00

37. Dental Impressions Alginate dental impressions are widely used at dental clinics around the world.

38. Algin Cooked Flan This formulation produces a custard-type dessert that does not require baking. This unique algin gel may be varied for new product concepts. QUANTITY INGREDIENTS GRAMS PERCENT Sugar, fine granular 72.985 93.571 DARILOID* QH alginate product 4.000 5.128 Salt, fine 0.500 0.641 Natural and artificial vanilla powder #8216 0.500 0.641 (David Michael) FD&C Yellow #5 0.012 0.015 FD&C Yellow #6 0.003 0.004 78.000 g 100.000% 1. Bring 472 ml (2 cups) whole milk to a boil in a one-quart saucepan. 2. Remove from heat and add package contents (78 g) while stirring with a fork. 3. Stir well for 1 minute. 4. Pour into serving dishes

40. Algin Water Gel KELTONE* HV is a specially clarified, low calcium sodium alginate which functions in dessert gels as a gelling agent by its reaction with calcium. The gel, formed at ambient or refrigerated temperatures, is stable and does not melt upon warming. QUANTITY INGREDIENTS GRAMS PERCENT Sugar, fine granular 76.88 90.443 KELTONE HV sodium alginate 3.00 3.529 Adipic acid (Solutia) 2.75 3.235 Sodium tripolyphosphate, anhydrous powder (Solutia) 1.50 1.765 Calcium carbonate #10 (Georgia Marble) 0.40 0.475 Artificial strawberry flavoring 59.389/AP 05.51 0.34 0.400 (Firmenich) Magnesium carbonate, powdered, USP TAC (Mallinckrodt) 0.10 0.118 FD&C Red #40 0.03 0.035 85.00 g 100.000 % PROCEDURE 1. Add dry ingredients (85 g) to 474 ml (2 cups) boiling water while stirring. 2. Stir briskly for one minute, pour into molds and refrigerate until chilled (about 2 hours). If complete cooling is not required, the refrigeration period may be shortened. Yields four 1/2 cup servings. The gel will also set at room temperature.

42. Unique Properties of Alginate Salts • Gel or Precipitate with Acid • React with Calcium Ions to: —Give Increased Viscosity— Form Heat Stable Gels —Form Insoluble Polymers ATM95 012.00

43. Algin Bakery Fillings - Benefits • Excellent Heat Stability • Hot or Cold Make-up • Superb Flavor and Color • Versatile (Solids, Fruit Levels, Texture) • No Tailing; Clean Depositing • Reduces the Rate of Moisture Transfer ATM95 025.00

47. Classification of Alginates • Alginic Acid • Alginate Salts • Propylene Glycol Alginates (PGAs) ATM95 012.00

48. OH OH OH COOH COOCH2CHCH3 COOCH2CHCH3 COOCH2CHCH3 O O O O O O O O OH OH OH OH OH OH OH OH Propylene Glycol Alginate Structure

49. Unique Properties of PGA • Tolerance to Low pH and High Calcium • Emulsification and Foam Stabilization • Sensitive to High pH and Heat ATM95 015.00

50. ++ • Tolerance to low pH and high Ca PGA Unique Properties Kelco CR Sem 4369-1